Vehicle cleaning and drying compositions

This invention relates to aqueous compositions that can be used in washing, rinsing or dewatering of vehicle surfaces. Such surfaces can be made of glass, rubber, painted surfaces, steel and aluminum wheels, plastic panels, thermoplastic/fabric or thermoplastic/fiber composite panels, plastic lenses and a variety of glass or metal composites and plastic trim pieces. The compositions of the invention are typically sprayed or wiped onto a vehicle surface for the purpose of removing a variety of soils common in the transportation, railway, airport, highway, etc. environment. Such soils are derived from fuels, lubricants, hydraulic and other functional fluids, dirt and grime, vehicle exhaust components, residue from prior cleaners, waxes, etc. Preferably, the compositions of the invention are used in either brushed, fabric contact or touchless systems. Such touchless systems involve a simple spray-on of the aqueous systems followed by an aqueous rinse leaving a clean vehicle surface, the surface comprising little or no residual cleaning composition or rinse.

Soiled vehicle surfaces have been cleaned for many years using a variety of compositions and methods. Such compositions can be as simple as solutions of organic dish soaps or common all-purpose utility cleaners. In commercial or industrial vehicle cleaning such as semi-automatic and completely automatic car washes, a variety of cleaning materials have been used in a cleaning system that can often contain a pre-rinse or pre-cleaning step, a cleaning step followed by a combination of one or more steps using waxes, rinses, anti-rust agents, mechanical dryers, etc. Such vehicle cleaning operations can be embodied in a retail cleaning operations designed for cleaning vehicles by personal owners or by car wash personnel. Such cleaning stations can also include stations operated by car rental agencies, retail car dealerships, automobile fleet operators, bus sheds, train depots, airplane maintenance buildings, etc.

One class of commonly available automotive cleaning materials contain a variety of anionic surfactants that is used in conjunction with compatible nonionic surfactants, sequestrants, waxes and other ingredients.

Hydrocarbon wax compositions, applied after the aforementioned cleaning step, promote a shiny finish and are blended to promote removal of water from the vehicle surfaces. Such waxes also often contain a wax with anionic or nonionic surfactants, anti-rust agents and other components that form a fully functional system that can dewater automobiles leaving a dry shiny finish.

A second class of waxing composition is commonly available including a typical formulation containing surfactants, solvents and a silicone wax-like material that forms a shiny surface. Silicones are well known, very hydrophobic materials that when used in vehicle waxing compositions with other components such as nonionic detergents, anti-rust agents, etc. to form a shiny, dry vehicle surface.

One common theme in the prior art cleaning compositions is an anionic material (typically a sulfonate or sulfate surfactant), while the prior art waxing compositions require hydrocarbon or silicone wax materials.

Amine compounds have also been commonly formulated in hydrocarbon containing and silicone containing wax compositions and compositions that contain both hydrocarbons and silicants. For example, Chestochowski et al., U.S. Pat. No. 3,440,063 teaches fatty amine-organic acid salts in car wash formulations. Baker et al., U.S. Pat. No. 3,592,669 discloses a hydrocarbon wax composition containing a fatty alkyl amine in a transparent film forming composition. Cifuentes et al., U.S. Pat. No. 5,258,063 discloses a gloss improving foam for use on vehicle surfaces. The film combines waxes with an alkyl cyclohexyl amine. Herring, GB 1,349,447 discloses a car polish composition comprising a paraffin wax combined with an alkyl diamine. Lastly, ABE, WO 92-22632 discloses a water repellent car window washing composition using a fatty amine acetate salt in combination with a hydrocarbon solvent and silicone wax in a complex formula containing a fluorocarbon active material. Fatty alkyl amines typically have the formula R-NH 2 wherein R is a hydrocarbon group that can have 1-3 unsaturated bonds but contain 6-24 straight chain carbon atoms.

Eriksson, WO 92-08823 discloses cleaning and degreasing agent containing an ethoxylated alkyl amine. Eriksson, EP 43360 teaches a metal corrosion protector comprising an ethoxylated amine composition. Lemin et al., GB 2,036,783 discloses a water repellent foam using a cationic dewatering agent comprising an ethoxylated amine that can also use an optional anti-static agent. Fatty ethanol amine amide compounds have been disclosed in, for example, in Bayless, U.S. Pat. No. 5,330,673 for use in adhesives and cleaners. Further, JP 06-145603 teaches a dewatering film form using triethanolamine and a hydrocarbon wax or silicone wax. JP 05-156289 teaches a vehicle cleaner containing short chain water soluble amines. Lastly, JP 03-024200 teaches a detergent for soil removal on vehicles using a short chain aqueous or nonaqueous amine.

Fox, U.S. Pat. No. 4,284,435 teach a car wash composition using an ethoxylated quaternary amine composition. Karalis et al., U.S. Pat. No. 4,864,060 teaches a car wash composition combining a quaternary ammonium compound and an amine oxide material. Betty, Jr. et al., U.S. Pat. No. 3,756,835 teaches an auto polish that combine a quaternary ammonium compound and an ethoxylated amine and a petroleum mineral oil. Tarr, U.S. Pat. No. 5,221,329 teaches a water repellent material used as a coating for aircraft comprising a quaternary ammonium compound and a saline compound. JP 03-262763 and JP 58-076477 disclose car wash compositions and anti-spotting coating compositions that can contain quaternary amine materials in combination with additives such as waxes, cationic surfactants, etc.

These prior art vehicle cleaning materials have had some success in the marketplace. However, the marketplace continually searches for materials having improved properties. Properties that can always use improvement include the gloss of the cleaned vehicle surface, the rate and amount of dewatering, water spotting on glass or painted surfaces, concentrate stability, solution clarity and overall ease of preparing aqueous dilutions from the aqueous concentrate materials. The marketplace has continually searched for improvements in aqueous systems containing organic cleaner materials that can have improved soil removal, improved gloss in the final vehicle surface, reduced spotting and improved dewatering. Lastly, the environmental compatibility of the hydrocarbon and silicone wax-like materials has been questioned in recent years. A substantial need exists to develop vehicle cleaners and rinses that can clean and shine with minimal aqueous residue in touchless or cloth or brush systems.

We have found that silicone and hydrocarbon wax-like materials can be substantially avoided in vehicle maintenance cleaning, drying or dewatering compositions if a fatty alkyl ether amine is used. We have found that in the conventional vehicle cleaning compositions conventional wax-like materials can be replaced in an aqueous cleaner, dewatering or drying agents by an alkyl ether amine or alkyl ether diamine of the formula

R--O--(R.sub.2).sub.n --NH--A

A═R.sub.3 NH.sub.2 or H

R 2 , R 3 =linear or branched alkyl

The ether amine and diamine compositions of the invention are typically formulated in liquid or solid aqueous concentrate materials in which the ether amine or diamine is combined with other compatible cleaning agents in a compatible aqueous concentrate that can be diluted with service water to form a material that can be readily applied (i.e.) sprayed onto a vehicle surface for the purpose of cleaning the vehicle surface leaving the vehicle with a shiny, glossy finish and with a minimum of water spotting or streaking. The amine is made compatable in the compositions of the invention using a stabilizing agent comprising a neutralizing acid or a nonionic surfactant. The stabilizing agent produces single phase ether amine compositions which can be clear solutions. A listing of the typical amine compounds used in the current art are shown in Table 11 (pages 38-39). In contrast to the prior art, anionic surfactants such as sulfates or sulfonates are not preferred and compositions of the invention are substantially free of amine reacting anionic materials. Such acid anionic materials like alkyl benzene sulfonates, alpha olefin sulfonates, and alcohol sulfates are believed to react with, neutralize and reduce the activity of the fatty amines of the invention.

For the purpose of this patent application, the term "vehicle" is intended to mean any transportation conveyance including automobiles, trucks, sport utility vehicles, buses, golf carts, motorcycles, monorails, diesel locomotives, passenger coaches, small single engine private airplanes, corporate jet aircraft, commercial airline equipment, etc. The term "touchless cleaning system" is directed to processes in which the cleaning materials are directly contacted with a vehicle surface comprising a painted surface, a thermal plastic composite surface, a glass surface, a rubber surface, or surfaces containing common automobile trim units for soil removal with a spray or flood with no added mechanical action used in soil removal. A "dewatering agent" promotes rapid and substantially complete drainage of aqueous residue on a vehicle surface. In use, an aqueous cleaner composition can be permitted to remain in contact with such surfaces for a relatively short period of time (less than 5 minutes) to promote soil removal. The aqueous systems are typically removed from the vehicle surface using an aqueous rinse followed by a dewatering agent. The term "hydrocarbon free wax" is intended to convey the concept that the materials of the invention do not contain a substantial proportion of any hydrocarbon that can participate in either soil removal, dewatering or providing a shiny coating to a vehicle painted surface. The term "silicone-free" is intended to convey the concept that the compositions of the invention are substantially free of silicone materials at concentrations typically available for the purpose of promoting a shiny surface, dewatering, water removal or spot or streak prevention. Trivial amounts of wax or silicone can be added within the scope of the invention. The term "anti-soiling" is intended to convey the concept that the materials of this invention aid in eliminating or repelling hard-surface water spots caused by soluble solids in rinse waters.

The vehicle cleaning compositions of the invention can be formulated in a variety of formats. The drying agent simply promotes dewatering of a vehicle surface. The composition can also take the form of a car wash cleaner composition that is formulated simply to be a soil removing agent that after removal of the cleaner leaves a shiny surface that can be dried to an attractive finish. The materials can also be prepared as a car wash formulation that can wash, dry and leave a shiny, dry surface. Basic formulations, which can be used in liquid or solid form, are found in the wax and silicone free formulas set forth below:

______________________________________

Wt % Preferred Wt %

______________________________________

Alkyl ether amine

1-55 2-8

Nonionic Surfactant

1-55 5-15

Amine oxide 0-25 5-15

Sequestrant 1-10 5-10

Base or Acid Adj to desired pH

Water Balance

Alkyl ether amine

1-55 5-15

Nonionic Surfactant

0-20 can be used

1-7

0.1-20 is useful

Acid To desired pH or

solution clarity

Water and/or Balance

solvent

NON-NEUTRALIZED AGENT (EMULSIFIED.sup.1 PHASE)

Alkyl ether amine

1-50 5-15

Nonionic (or blended

1-20 3-10

nonionic) Surfactant

Water and/or solvent

Balance

Alkyl ether amine

0.1-50 2-10

Nonionic Surfactant

1-20 5-15

Fatty amine ethoxylate

0-20 1-10

Alkyl dimethyl amine-oxide

0.1-20 5-15

Sequestrant 0.5-20 5-10

Solvent (glycol ether)

1-15 2-10

Base (pH adjustment)

0.1-5 1-3

Silicate (aluminum

0.1-5 0.5-3

protection)

Solidification agent

Optional 0.1-30.sup.2

Water Balance Balance

______________________________________

.sup.1 Amine in water, dispersed amine in continuous aqueous phase.

.sup.2 Solidification agent is used only if solid formulation is needed.

In general, the formulations can be liquid or solid and can contain the fatty ether amine compositions of the invention in combination with a variety of other materials useful in the manufacture of vehicle cleaning and dewatering agents including nonionic surfactants, amine oxide surfactants, sequestrants, acidic materials, basic materials, solvents, and a variety of other useful materials such as dyes, fragrances, thickening agents, foaming surfactants and others. Conventional hardeneing or solidification agents can be used including urea, PEG materials, nonionics, etc.

The vehicle maintenance compositions of the invention can contain a fatty ether amine compound of the formula:

R--O--(R.sub.2).sub.n --NH--A

A═R.sub.3 NH.sub.2 or H

R 2 , R 3 =linear or branched alkyl

Preferred amines include tetradecyloxypropyl-1,3-diaminopropane; a C 12-14 alkyl oxypropyl-1,3-diaminopropane; a C 12-15 alkyloxypropyl amine and other similar materials that can be obtained in the market place under the tradename of TOMAH® DA19, DA18, DA17, DA1618, DA14, PA19, PA17, PA16, PA14, PA1214, etc.

Nonionic surfactants useful in cleaning compositions, include those having a polyalkylene oxide polymer as a portion of the surfactant molecule. Such nonionic surfactants include, for example, chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other like alkyl-capped polyethylene glycol ethers of fatty alcohols; polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated ethylene diamine; alcohol alkoxylates such as alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates, and the like; dodecyl, octyl or nonylphenol ethoxylates, polyoxyethylene glycol ethers and the like; carboxylic acid esters such as glycerol esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids, and the like; carboxylic amides such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, and the like; and polyalkylene oxide block copolymers including an ethylene oxide/propylene oxide block copolymer such as those commercially available under the trademark PLURONIC™ (BASF-Wyandotte), and the like; and other like nonionic compounds. Silicone containing nonionic surfactants such as the ABIL B8852 or Silwet 7602 can also be used. The following materials are particularly preferred: fatty amines (coco, tallow, etc. amines) ethoxylated with 2 to 18 moles of ethylene oxide (EO), substituted amines of the formula: R 1 --O--R 2 --NH--R 2 --NH 2 , or ethoxylated species thereof, wherein R 1 is a fatty group, each R 2 is independently a C 1-6 alkylene; a poloxamine, an (EO) x (PO) y --NH--R 2 --NH 2 , wherein R 2 is a C 1-6 alkylene group; C 9-14 alcohol ethoxylated with 3 to 10 moles of ethylene oxide (EO), coco alcohol ethoxylated with 3 to 10 moles EO, stearyl alcohol ethoxylated with 5 to 10 moles EO, mixed C 12 -C 15 alcohol ethoxylated with 3 to 10 moles EO, mixed secondary C 11 -C 15 alcohol ethoxylated with 3 to 10 moles EO, mixed C 9 -C 11 linear alcohol ethoxylated with 3 to 10 moles EO and the like. It is preferred that the nonionic have from 8 to 12 carbon atoms in the alkyl group. When this preferred alkyl group is used the most preferred nonionic is the mixed C 9 -C 11 alcohol ethoxylated with 3-7 moles EO.

An important nonionic surfactant can comprise an amine oxide. Such materials are made by oxidizing a t-alkyl amine to an amine oxide. Preferred amine oxides are typically C 6-28 alkyl dimethylamine oxides. Representative examples of such amine oxides are lauryl dimethylamine oxide, dodecyl dimethylamine oxide, tetradecyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, dodecyl diethylamine oxide, bis(2-hydroxypropyl)tetradecylamine oxide, etc.

Typical aqueous compositions combined with service water can contain the sequestrant to reduce the undesirable effects of typically di- and trivalent metal cations. Such cations can reduce the effect of a variety of the organic components of the formulations of the invention and can promote water spotting. Suitable chelating agents include both inorganic and organic chelating agents. Inorganic silicates, carbonates, phosphates, and borates are examples. Organic chelating agents include trisodium nitrilotriacetate, trisodium hydroxyethylethylenediamine triacetate, tetrasodium ethylenediamine tetraacetate, polyacrylic acid sodium salts and other sequestering or chelating agents well known in the industry.

The compositions of the invention can contain an acidic or basic material that can act to neutralize either a basic or acidic pH, respectively. Such basic materials include amines, sodium hydroxide, sodium silicate materials, etc. These materials can act as an alkaline builder, soil disbursement and buffering agent. The preferred silicate materials also act as an aluminum protectant that can reduce the impact of the chemicals of the invention on exposed aluminum surfaces. The alkaline builder material should be present in amounts sufficient to obtain a pH approximately neutral (i.e., about 6 to 10, preferably 6-9). A variety of typically weak or mild acids can be used to neutralize and solubilize the basic compositions to a variety of pH's. Such acids include acetic acid, hydroxyacetic acid, phosphoric acid, citric acid, and other typical acids used in the manufacture of cleaning compositions.

The formulations of the invention can contain a solvent material. The preferred chemistry requires no solvent. Preferred solvents comprise alcohols, glycols, glycol ether materials. Such materials tend to have aliphatic moieties containing 2 to 6 carbon atoms. Examples of such materials include ethanol, propanol, isopropanol, butanol, 2-butanol, 2-methyl-2-propanol, butoxy diglycol, ethoxy diglycol, polypropylene glycol, ethylene glycol methyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol n-butyl ether, butoxy ethanol, phenoxy ethanol, methoxy propanol, propylene glycol, n-butyl ether, tripropylene glycol, n-butyl ether, propylene glycol, hexylene glycol and other similar oxygenated solvents.

Run # Amine Compound lution pH.sup.2

(grams)

control).sup.3

______________________________________

1 control (no amine).sup.4

2.8 4.03 --

2 control (no amine).sup.4

10.8 5.62 --

Composition of the Invention

3 C.sub.12-15 linear ether diamine.sup.5

2.6 0.12 97%

4 C.sub.12-15 linear ether diamine.sup.5

10.6 0.23 96%

5 C.sub.12-15 linear ether

2.3 0.08 98%

monoamine.sup.6

6 C.sub.12-15 linear ether

10.7 0.16 97%

monoamine.sup.6

7 car wash I.sup.7 + PA-19

11.3 0.18 97%

8 car wash II + PA-19.sup.6

11.3 0.15 97%

9 car wash II.sup.8 + DA-19.sup.5

11.2 0.21 96%

10 car wash II.sup.8 + DA-1618.sup.9

11.1 0.26 95%

11 acid cleaner I.sup.10 + DA-19.sup.5

2.7 0.06 99%

12 BELIEVE.sup.11 10.4 4.92 12%

13 ZIP WAX CAR WASH -

8.7 5.03 10%

SHINE.sup.12

14 SUDDEN SHINE CLEAN

7.0 5.61 <1%

& SHINE.sup.13

15 ethoxylated alkyl amine I.sup.14

3.0 3.98 1%

16 ethoxylated alkyl amine II.sup.15

10.0 5.87 0%

17 alkyl dimethyl benzyl

2.7 3.69 8%

quat.sup.16

18 alkyl dimethyl benzyl

9.2 5.43 3%

quat.sup.16

19 alkyl amine acetate.sup.17

4.7 0.55 87%

20 alkyl amine/diamine

9.8 0.38 78%

mixture.sup.18

______________________________________

.sup.1 The test amines or ammonium formulas were made up as 3 wt % amine

in the test solutions. The commercial products (lines 17, 18, 19) were no

prediluted. Each formula was tested using 12" × 12" glass squares

which were treated with 1.5 vol % aqueous dilutions of the aforementioned

solutions, at various pH's, then rinsed under well water for 5 seconds,

and finally drained for 5 seconds. The residual surface water was

determined gravimetrically.

.sup.2 The pH was adjusted with glycolic or acetic acids.

.sup.3 Water removal was calculated using 100 × (1 - residual water

was control sample line1 for test solutions at pH's <7.0 and control

sample line2 for pH's >7.0.

.sup.4 Well water neutralized with glycolic acid or NaOH; i.e., no amines

or ammonium compounds present.

.sup.5 Tomah DA19.

.sup.6 Tomah PA19.

.sup.7 Car wash I = 3% ethoxylated amine, 7% EDTA, 3% Tomah PA19, 3% amin

oxide, 10% nonionic surfactant, 2% silicate, 1% NaOH, and the remainder a

fragrance/water.

.sup.8 Car wash II = 6% monoethanol amine MEA, 5% EDTA, 8% betaine

surfactant, 20% glycol solvents, 6% LAS, 3% amines, remainder as

fragrance/water.

.sup.9 Tomah DA1618.

.sup.10 Acid cleaner I = 7% sulfamic acid, 7.5% citric acid, 12% amine

oxide, 9% glycol solvents, 10% phosphoric acid, remainder as

fragrance/dye/water.

.sup.11 BELIEVE is an industrial car wash detergent for high pressure

washing, from S. C. Johnson Co., Rascine, WI.

.sup.12 ZIP WAX is a commercial car wash detergent, from Turtle Wax, Inc.

Chicago, IL.

.sup.13 SUDDEN SHINE is a consumer car shine and windshield dewatering

aid, from Plastone Co., Bedford Park, IL.

.sup.14 Prior art using ethoxylated alkylamines; JP 63048398, Ger. Offen

DE 4,412,380, GB 2036783 using Exxon ET5.

.sup.15 Prior art as in ref. 14, but using Varonic K215.

.sup.16 Prior art using quats like WO 9222632, US 4,284,435, JP 58076477

using 0372 from Ecolab.

.sup.17 Prior art like WO 9222632, US 3440063 using Armene OL.

.sup.18 Prior art like US 3440063 using an amine mixture = 2:1:0.5 of

Duomene OL:Duomene CD:Armene OL.

Measurement of Car Wash Brush Lubricating Action

The dewatering fatty alkyl ether amines of the invention can also impart a lubricious component to the polymeric brush heads used in mechanical transportation washers. This friction reduction is deemed important for minimizing scratching and wear in mechanical car wash systems employing polymeric bristle brushes to enhance auto soil removal. Recognizing a near logarithmic scale for the relative coefficient of friction (COF), the results show the remarkable improvement in lubricity of this patent (lines 1-5) vs. the prior art (lines 6-7). The COF's below 1.00 are indicative of minimal drag, while those of the prior art above 1.00 impart considerable wear to hard surfaces, and those above ˜1.3 COF indicate extreme wear.

______________________________________

Lubricity of Polymeric Washing Brush Surfaces.sup.1

Relative

Friction Wash Coefficient of

Test # Formula Test Amine

Friction.sup.2

______________________________________

1 car wash DA-1618 0.90

formula 1.sup.3

2 car wash DA-1618 0.99

formula 2.sup.4

3 car wash DA-1618 0.97

formula 3.sup.5

4 car wash DA-18 0.95

formula 4.sup.6

6 BELIEVE CAR benzyl quat

1.33

WASH.sup.8

7 ZIP WAX CAR none 1.22

WASH.sup.9

______________________________________

.sup.1 Samples for lubricity measure were diluted to 0.1% (unless

otherwise stated) with distilled water containing 200 ppm NaHCO.sub.3, an

streamed along the perimeter of a polished stainless steel plate measurin

20.5 cm in diameter. The plate was connected to an electric motor, and

rotated at an even rate when switched on. A polyester disk weighing 238 g

was attached to a load cell and placed on the plate in the area wetted by

the lubricant solution. When the electric motor was switched on, the disk

glided freely on the plate. The drag between the polyester surface and th

stainless steel plate was detected by the load cell, and transferred to a

chart recorder. To assure consistency of the test method, the drag from a

standard reference anionic wash detergent solution was measured before an

after each trial run, and the value obtained therefrom arbitrarily

assigned a coefficient of friction of 1.00. Each trial run was referenced

to the fatty acid lubricant trials, thus the results are reported as a

relative coefficient of friction vs. this standard.

.sup.2 Control car wash concentrate for lubricity COF reference: 2.0%

hydrotrope, 4.0% SXS, 10.0% EDTA, 8.0% nonionic surfactant, 13.5% TEA,

10.0% anionic surfactants, and the remainder soft water.

.sup.3 7.0% glycols, 9.0% amine, 4.0% neutralizing acid, 2% linear

nonionic surfactant, and the remainder as soft water.

.sup.4 7.0% glycols, 9.0% amine, 4.0% neutralizing acid, 2% secondary

nonionic surfactant, and the remainder as soft water.

.sup.5 7.0% glycols, 9.0% amine, 4.0% neutralizing acid, 1% secondary

nonionic surfactant, and the remainder as soft water.

.sup.6 7.0% glycols, 6.0% amine, 4.0% neutralizing acid, 10% secondary

nonionic surfactant, and the remainder as soft water.

.sup.8 BELIEVE is an industrial car wash detergent for high pressure

washing, from S. C. Johnson Co., Rascine, WI.

.sup.9 ZIP WAX is a commercial car wash detergent, from Turth Wax, Inc.,

Chicago, IL.

Measurement of Car Wash Spotting by Hard Waters

A test was performed to determine the ability of coatings of the fatty amines of the invention to repel or minimize ever present, and unsightly, water spots in detergent products (like windshield dewatering aids). Because this soil, on a windshield, is one of the more visual for a consumer, any control would be quite beneficial. Tables 6 and 7 list evaluations for various amines, 2 control samples, and 4 examples of competitive art for hard water scale formation. The test was conducted by applying the amine coating to a glassy-ceramic titled surface, except for the control samples, then followed by 15 well water rinses, with 30-minute drying between rinses. The tiles were visually evaluated at the end of the 15 cycles on a scale of 1-4 (see reference #2 in Table 6).

The current results show that the longer chain (>C12) alkyl-ether amines function extremely well as hard-surface water spot inhibitors while the prior art is less effective, and sometimes comparable to no treatment at all.

______________________________________

Anti-Scaling Properties of Amine Coatings

Using Well Water

Final Well

Amine Anti- Test Solution

Water Spot

Run # Sealant pH.sup.1 Rating.sup.2

______________________________________

Compositions of the Invention

1 C.sub.12-15 linear

2.6 1

ether diamine.sup.3

2 C.sub.12-15 linear

6.0 1

ether diamine.sup.3

3 C.sub.12-15 linear

10.5 1

ether diamine.sup.3

4 C.sub.12-14 linear

2.2 1

ether diamine.sup.4

5 C.sub.12-14 linear

8.8 1

ether diamine.sup.4

6 branched 3.0 2

isotridecyl

ether diamine.sup.5

7 branched 8.0 2

isotridecyl

ether diamine.sup.5

8 C.sub.8-10 linear

8.4 3

ether monoamine.sup.6

9 C.sub.8-10 linear

3.2 4

ether monoamine.sup.6

10 prior art.sup.7 ;

8.0 2

ethoxylated

alkyl amine.sup.8

11 prior art.sup.9 ;

2.7 4

benzyl quat.sup.10

12 prior art.sup.9 ;

7.4 4

benzyl quat.sup.10

13 none (control

3.1 4

A).sup.11

14 none (control

8.6 4

B).sup.11

______________________________________

.sup.1 pH adjusted with glycolic acid.

.sup.2 1 = no to few water spots, small diameter, easily removed by

wiping.

2 = a few water spots, medium in size, easily removed by wiping.

3 = a few to many water spots, large in size, difficult to remove by

wiping.

4 = many water spots, large in size, difficult to remove, dirty looking.

.sup.3 Tomah DA19.

.sup.4 Tomah DA1618.

.sup.5 Tomah DA17.

.sup.6 Tomah PA1214.

.sup.9 current art using quats; JP 58076477.

.sup.10 Ecolab Q372 quat.

.sup.11 Control = a tile cleaned with Chlorox cleanser, rinsed five times

and dried.

6 prior art

cocoamine 3 -- -- -- -- -- cloudy

I.sup.4,5,6

7 prior art

oleylamine 3 -- -- -- -- -- cloudy

I.sup.4,5,6

9 prior art

N-oleyl-1,3-diamino

8 hazy/

hazy/

cloudy

cloudy

cloudy

--

III.sup.3,5,6

propane opaque

opaque

10 prior II.sup.3,5,6

N-oleyl/cocoa-1,3-

4/4

clear

clear

clear

cloudy

cloudy

--

diamino propane

11 prior art

N-oleyl/cocoa-1,3-

4/4

clear

clear

clear

cloudy

cloudy

--

III.sup.3,5,6

diamino propane

12 prior art

N-oleyl/coco-1,3-

4/2

cloudy

clear

clear

cloudy

cloudy

--

III.sup.3,5,6

diamino propane

__________________________________________________________________________

.sup.1 Challenge water prepared by adding 500 ppm Na.sub.2 SO.sub.4 and

500 ppm NaCl to softened water.

.sup.2 1% detergent solutions adjusted to pH 5, 6, 7, 8, 9 or 10 with

dilute acetic acid or dilute KOH.

.sup.3 Composition of formulas: 8.0% total amines, 10.0% hydrotrope, 1.8%

acetic acid, 10.0% nonionic surfactant, and 70.2% water.

.sup.4 Composition of formula: 3.0% amine, 7.0% EDTA, 12.7% alcohol and

alkylamine nonionic surfactants, 2.5% builder, 3.2% amine oxide.

.sup.5 Prior art as taught by DD 91104, US 3440063, and DE 3439440.

.sup.6 Prior art examples presented in US 5441654, and US 5062978.

Test Procedure for Concentrate Flammability

Windshield dewatering samples representing the proposed invention and the prior art were tested for consumer safety by pouring 1 gram of the formula concentrate on a watch glass slide and heating with a propane flame. The results of Table 10 show a subjective rating of the products, and demonstrate the aqueous fatty alkyl ether amines to be much safer for general use over the prior art. The current invention samples (test 1-3) went to dryness, while all the prior art examples (4-7) supported rapid to instantaneous combustion.

______________________________________

Flammability of Window Dewatering Aids.sup.1

Test # Wash Formula Flammability

______________________________________

Current Art

1 car dewatering flash point >180° F.

formula 3.sup.2

2 car dewatering flash point >180° F.

formula 4.sup.2

3 car dewatering flash point >180° F.

formula 5.sup.2

4 SUDDEN SHINE.sup.3

flammable

5 RAIN-X.sup.4 very flammable

6 prior art I.sup.5

very flammable

7 prior art II.sup.6

flammable

______________________________________

.sup.1 Samples representing the proposed invention and the prior art were

tested for consumer safety by pouring 1 gram of the formula concentrate o

a watch glass slide and heating with a propane flame. The results show a

subjective rating of the products.

.sup.2 Same test samples as noted in Table 5.

.sup.3 SUDDEN SHINE is a commercial auto dewatering aid from Plastone Co.

Chicago, IL.

.sup.4 RAINX is a commercial auto windshield dewatering aid, from

.sub.----, Phoenix, AZ.

.sup.5 prior art as taught in DD 91104.

.sup.6 prior art as taught in DE 3439440.

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Vendor Trade Name Chemical Name R group

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Commercially Available Diamines and Ether Diamines

Cited in the Examples

Tomah DA-19 C.sub.12-15 linear,

alkyloxypropyl-

C.sub.12 H.sub.25 /C.sub.15 H.sub.31

1,3-diamino

propane

Tomah DA-18 tetradecyloxy-

linear,

propyl-1,3 diamino

C.sub.14 H.sub.29

propane

Tomah DA-17 isotridecyloxyprop

branched,

yl-1,3 diamino

C.sub.12 H.sub.25

propane

Tomah DA-1618 C.sub.12-14 linear,

alkyloxypropyl-1,3

C.sub.12 H.sub.25 /C.sub.14 H.sub.27

diamino propane

Tomah DA-14 isodecyloxypropyl-

branched,

1,3 diamino C.sub.10 H.sub.21

propane

Akzo Duomeen OL N-oleyl-1,3 linear,

diamino propane

C.sub.18:1 H.sub.35

Akzo Duomeen CD N-coco-1,3 diamino

linear

propane C.sub.12-14 H.sub.25-29

Commercially Available Amines and

Ether Amines Cited in the Examples

Tomah PA-19 C.sub.12-15 alkyloxypropyl

linear,

amine C.sub.12 H.sub.25 /C.sub.15 H.sub.31

Tomah PA-17 isotridecyloxypropyl

branched,

amine C.sub.13 H.sub.27

Tomah PA-16 isododecyloxypropyl

branched,

amine C.sub.12 H.sub.25

Tomah PA-14 isodecyloxypropyl

branched,

amine C.sub.10 H.sub.21

Tomah PA-1214 octyl/decyloxypropyl

branched,

amine C.sub.8 H.sub.17 /C.sub.10 H.sub.21

Akzo Armeen OL oleylamine linear,

C.sub.18:1 H.sub.35

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Solid Wash and Dry Car Wash Formula

The following formulation was manufactured into a solid block car wash formulation that could be dispensed by spraying the solid composition with water in a dispenser creating a concentrate solution that can be then conveyed to a use locus in a vehicle cleaning station. The formulation is made by introducing ingredients 1 through 4 in a heated stirred tank of appropriate size. After the material is heated and mixed to a temperature of about 75° C., ingredients 5 and 6 are added and mixed until uniform. In the uniform mixture, item 7 is added and mixed until uniform. After equilibration is achieved, powdered ingredients 8 and 9 are slowly added to avoid caking or lumping. The composition is stirred until uniform and charged in 8 pound portions to polyethylene bottles which can then be cooled and solidified. The bottles are ideal for capping, distribution and use at a vehicle cleaning station. The solid formulation achieves results similar to the liquid formulation set forth above.

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Formula %

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1 Nonionic PEG ether of a

12.0

C.sub.12-15 alcohol Neodol 25-7

2 Nonionic PEG ether of a

17.0

C.sub.6-11 alcohol Neodol 91-6

3 EDTA (Liq 40%) 12.0

4 Urea 22.0

5 Ether amine Tomah DA-1618

6.0

6 Varonic K-215 9.0

7 Admox 14815 8.0

8 EDTA (Pwd) 11.0

9 G.D. Silicate 3.0

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The above specification, examples and data provide a complete description of the manufacture and use of the composition of the invention. Since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended.